Extended Mo 3 IV -Polyoxometalates: 1D-[Mo 6 IV Mo 4 VI Ge 2 ZnO 31 py 9 (H 2 O)] 4- and 2D-[Mo 3 IV Mo 9 VI Zn 6 P 7 O 56 py 8 ] + (py = Pyridine).

The first examples of extended Mo 3 IV -polyoxometalates (Mo 3 IV -POMs), 1D-H 2 [Ge 2 Mo 6 IV Mo 4 VI O 31 Zn(H 2 O)py 9 ]·2Hpy·HOCH 2 CH 2 OH • 4H 2 O(H 2 [ 1 ]·2Hpy • glycol·H 2 O) and 2D-[P@Mo 3 IV Mo 9 VI Zn 6 (PO 4 ) 6 O 32 py 8 ]Cl·2py·7H 2 O ([ 2 ]·Cl • 2py·7H 2 O), were prepared through the solvothermal partial oxidation of [Mo 3 IV O 2 (O 2 CCH 3 ) 6 (H 2 O) 3 ]ZnCl 4 in py/H 2 O containing glycol (for 1 ) or H 3 PO 4 (for 2 ). They were characterized by X-ray crystallography and elemental analyses. Their electronic structure and bonding were discussed on the basis of density functional theory (DFT) theoretical calculations. X-ray photoelectron spectroscopy, IR/UV-vis spectra, powder X-ray diffraction, thermal gravimetric analysis, and mass spectrometry were also performed and discussed for 2D- 2 .